Novel phosphorous esters of substituted phenols have been found to exhibit insecticidal and miticidal activity.
|
2. A method in accordance with
O-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphate.
3. A method in accordance with
O-ethyl-S-n-propyl-O-[2-(acetylhydrazonomethyl)phenyl]thiophosphate.
4. A method in accordance with
O-ethyl-S-n-propyl-O-[2-(methoxycarbonyl-hydrazonomethyl)phenyl]thiophospha
te.
5. A method in accordance with
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminomethyl)phenyl]thiophospha
te.
6. A method in accordance with
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semi-carbazonomethyl)phenyl]thiophosp
hate.
7. A method in accordance with
O-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyloxyiminomethyl)phenyl]thiophosph
ate.
8. A method in accordance with
O-ethyl-S-n-propyl-O-[2,6-dibromo-4-(methoxyiminomethyl)phenyl]thiophosphat
e.
11. A method in accordance with
O-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)-2-naphthyl]-thiophosphate.
24. A composition in accordance with
O-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl), phenyl]thiophosphate.
25. A composition in accordance with
O-ethyl-S-n-propyl-O-[2-(acethylhydrazonomethyl)phenyl]thiophosphate.
26. A composition in accordance with
O-ethyl-S-n-propyl-O-[2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphat
e.
27. A composition in accordance with
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminomethyl)phenyl]thiophospha
te. 28. A composition in accordance with
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosph
ate.
29. A composition in accordance with
O-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyl-oxyiminomethyl)phenyl]thiophosp
hate.
30. A composition in accordance with
O-ethyl-S-n-propyl-O-[2,6-dibromo-4-(methoxyiminomethyl)phenyl]thiophosphat
e.
33. A composition in accordance with
O-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)2-naphthyl]thiophosphate.
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This invention relates to novel insecticidal and miticidal phosphorous esters of substituted phenols. This invention also relates to pesticidal compositions for controlling insects and mites, as well as to methods of controlling insects and mites by subjecting them to an insecticidally or miticidally effective amount of a compound of this invention.
The novel compounds of this invention are compounds of the formula: ##STR1## wherein: X is oxygen or sulfur;
R1 and R2 are individually lower alkyl groups;
Z is hydrogen, alkyl, alkoxy, halo, nitro, cyano, aryl, aryloxy, alkylthio, amino, alkylamino, dialkylamino, a C3 to C8 cycloalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylaminoalkyl, dialkylaminoalkyl, trihaloalkyl, or divalent alkylene group of 3 to 5 carbon atoms wherein the formed 6-membered ring may optionally be aromatic or substituted aromatic;
n is 1, 2 or 3;
Y is: ##STR2## wherein: R3 and R4 are individually hydrogen, lower alkyl, lower alkenyl, or aryl;
3. NOR5
wherein:
R5 is substituted or unsubstituted lower alkyl, aryl, or arylalkyl; ##STR3## wherein: R6 is lower alkyl, alkoxy, aryloxy, substituted alkyl, cycloalkyloxy, furanyl, or phenylureido;
5. oxygen;
6. CR7 R8
wherein:
R7 and R8 are hydrogen, alkyl, cyano, or halo; ##STR4## wherein: R9 is lower alkyl;
wherein:
X1 is oxygen or sulfur;
with the proviso that when Y is oxygen, Z is not a lower alkyl, halo, or hydrogen.
Generally, the preferred compounds of this invention are those
wherein:
R1 is ethyl;
R2 is n-propyl;
Y is ##STR5## Z is hydrogen, a 4 carbon, divalent alkylene group forming a 6-membered aromatic ring or halo;
n is 1, 2 or 3; and
X is oxygen.
The most preferred compounds of this invention are the following:
O-ethyl-S-n-propyl-O-[1-(semicarbazono-methyl)-2-naphthyl]-thiophosphate;
O-ethyl-S-n-propyl-O-[2-(semicarbazono-methyl)phenyl]-thiophosphate;
O-ethyl-S-n-propyl-O-[2-(acetylhydrazonomethyl)phenyl]-thiophosphate;
O-ethyl-S-n-propyl-O-[2-(methoxycarbonyl-hydrazonomethyl)phenyl]thiophospha te;
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminomethyl)phenyl]thiophospha te; and
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosph ate.
O-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyloxyiminomethyl)phenyl]thiophosph ate.
O-ethyl-S-n-propyl-O-[2,6-dibromo-4(methoxyiminomethyl)phenyl]thiophosphate .
The novel phosporous esters of substituted phenols of this invention can be conveniently prepared by the two general reaction methods or modifications thereof set forth below: ##STR6##
In these reaction sequences one equivalent of the parent phenol reacts with an appropriate chlorophosphorous compound in the presence of at least one equivalent of an acid acceptor (base), preferably in an inert solvent. The aldehyde is reacted with at least one equivalent of YH2 in an inert solvent.
In general any organic solvent that is inert to the reactants or reaction conditions may be employed in the reaction schemes shown above. Illustrative solvents which are suitable in the phosphorylation reaction are saturated, unsaturated, and aromatic hydrocarbons, e.g., hexane, cyclohexane, octane, cyclohexene, dodecane, naphtha, decalin, kerosene, cycloheptane, benzene, toluene, xylene, naphthalene, or the like; ethers such as dioxane, tetrahydrofuran, diethyl ether, tetrahydropyran, 1,2-dimethoxybenzene, the dialkyl ethers of ethylene glycol, of propylene glycol, or chlorinated aliphatic hydrocarbons such as chloroform, dichloromethane, 1,1-di-chloroethane, carbon tetrachloride, and the like.
The phosphorylation reactions may also be conducted in a solvent which functions as an acid acceptor. Illustrative of such solvents are N,N-dimethylaniline, pyridine, alpha-picoline, any lutidine, collidine or similar aromatic or hetero-cyclic tertiary amine compound.
In general solvents used to effect condensation (--CHO→--CH═Y) include water, ethers such as dioxane, tetrahydrofuran, dialkyl ethers of ethylene glycol, alcohols--such as methanol, ethanol, isopropanol, esters such as ethyl acetate and combinations thereof.
The acid acceptor utilized in these reactions can be either organic or inorganic bases. Illustrative of organic bases that are useful acid acceptors are tertiary amines such as triethylamine, pyridine, trimethylamine, 4-dimethylaminopyridine, or 1,4-diazabicyclo[2.2.2]octane; bases such as sodium carbonate, potassium carbonate, sodium acetate, and sodium hydroxide are illustrative of useful inorganic bases.
The reactions set forth above are neither temperature nor pressure sensitive and can be conducted over a broad range of temperatures and pressures to yield the desired product. Preferably these reactions are conducted at a temperature of from about -40°C to about 140°C and at atmospheric or autogeneous pressure.
The phosphorous halides utilized as reactants in the above schemes generally are known materials in the art and can be obtained from commercial sources or prepared in accordance with conventional methods known to those skilled in the art.
The substituted phenols utilized as starting materials in the above schemes are known compounds or can be prepared in accordance with conventional methods known to those skilled in the art.
The following examples are illustrative of the methods of preparing the novel compounds of this inventions.
PAC Preparation of O-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphateA 100 ml four-neck round bottom flask, equipped with a magnetic stirring bar, water condenser, and thermometer, was charged with 3.7 grams (0.03 mole) salicyaldehyde, 4.0 grams (0.04 mole) triethylamine and 50 ml anhydrous ether. The resulting solution was stirred at room temperature during which time 5.9 grams (0.029 mole) o-ethyl-S-n-propyl phosphorochloridate was added dropwise. The material was stirred until the reaction was complete at which time the resulting precipitate was filtered. The ether layer was washed with water, dried over anhydrous magnesium sulfate, filtered and concentrated to yield the substituted phenol phosphate.
1.3 grams (0.0115 mole) of semicarbazide hydrochloride; 1.25 g (0.015 mole) sodium acetate; and 10 ml of water was added to a 250 ml Erlynmeyer flask. The contents were heated to 57°C at which time 2.5 g (0.0085 mole) O-ethyl-S-n-propyl-O-[2-formylphenyl]thiophosphate dissolved in 5 ml of ethyl alcohol was added. The precipitate was filtered, washed with water, acetone, and ethyl ether. The material was then dried in a vacuum oven to yield 1.2 g (40.9Δ yield) of product having a melting point of 127°-129°C
Calcd. for C13 H20 N3 O4 PS: C, 45.22; H, 5.80. Found: C, 45.36; H, 5.72.
PAC Preparation of O-ethyl-S-n-propyl-O-[4-(methoxyiminomethyl)-phenyl]thiophosphateMethoxyamine hydrochloride (4.93 g, 59 mmol), sodium acetate (5.55 g, 66 mmol) and water (20 ml) were warmed to 50°C and a solution of O-ethyl-S-n-propyl-O-(4-formylphenyl)thiophosphate (11.39 g, 39.5 mmol) in ethanol (10 ml) was added at once. The solution was cooled to room temperature. After 3 hours, the solution was diluted with water (100 ml) and extracted three times with ethyl acetate. The combined organic extracts were washed once with water and dried over magnesium sulfate. Filtration and concentration under reduced pressure afforded the desired product: 9.63 g yellow oil.
Calcd. for C13 H20 NO4 PS: C, 49.20; H, 6.35. Found: C, 49.35; H, 6.42.
The following compounds are illustrative of this invention all of which can be conveniently prepared by the processes of this invention simply by selecting appropriate starting materials.
O-ethyl-S-n-propyl-O-[3-(isopropoxycarbonylhydrazonomethyl)-phenyl]thiophos phate
O-ethyl-S-n-propyl-O-[2-(n-propyloxycarbonylhydrazonomethyl)-phenyl]thiopho sphate
O-ethyl-S-n-propyl-O-[2-chloro-3-(ethoxycarbonylhydrazono-methyl)phenyl]thi ophosphate
O-ethyl-S-n-propyl-O-[3-chloro-5-(methoxycarbonylhydrazono-methyl)phenyl]di thiophosphate
O-ethyl-S-n-propyl-O-[4-chloro-2-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-nitro-2-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-methoxy-4-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-(methoxyiminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-nitro-3-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-methoxy-6-nitro-4-(semicarbazonomethyl)phenyl]thiop hosphate
O-ethyl-S-n-propyl-O-[2-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphat e
O-ethyl-S-n-propyl-O-[2-(t-butoxycarbonylhydrazonomethyl)phenyl]thiophospha te
O-ethyl-S-n-propyl-O-(2-formyl-4-nitrophenyl)thiophosphate
O-ethyl-S-n-propyl-O-(3-formyl-4-nitrophenyl)thiophosphate
O-ethyl-S-n-propyl-O-(4-formyl-2-methoxy-4-nitrophenyl)thiophosphate
O-ethyl-S-n-propyl-O-(4-formyl-3-methoxyphenyl)thiophosphate
O-ethyl-S-n-propyl-O-(1-formyl-2-naphthyl)thiophosphate
O-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)-2-naphthyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-chloro-1-(semicarbazonomethyl)-2-naphthyl]thiophosp hate
O-ethyl-S-n-propyl-O-[1-(semicarbazonomethyl)-2-(5',6',7',8'-tetrahydronaph thyl)]thiophosphate
O-ethyl-S-n-propyl-O-[1-(1'-semicarbazonoethyl)-2-naphthyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-butyl-O-[1-formyl-2-naphthyl)thiophosphate
O-ethyl-S-n-propyl-O-[1-(thiosemicarbazonomethyl)-2-naphthyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(thiosemicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(2',2'-dicyanovinyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(trimethylammoniumacetylhydrazonomethyl)phenyl]thio phosphate chloride
O-ethyl-S-n-propyl-O-[4-(1'-methoxyiminoethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-(1'-ethoxycarbonylhydrazonoethyl)phenyl]thiophospha te
O-ethyl-S-n-butyl-O-[2-chloro-4-(1'-ethoxycarbonylhydrazonoethyl)phenyl]thi ophosphate
O-ethyl-S-n-butyl-O-[4-(2',2'-dicyanovinyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxyiminoethyl)phenyl]-thiophospha te
O-ethyl-S-n-propyl-O-[4-(2,6-dichlorobenzyloxyiminomethyl)phenyl]thiophosph ate
O-ethyl-S-n-phenyl-O-[2,6-dibromo-4-(methoxyiminomethyl)phenyl]thiophosphat e
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophosph ate
O-ethyl-S-n-propyl-O-[2,6-dichloro-4-(methoxycarbonylhydrazonomethyl)phenyl ]thiophosphate
O-ethyl-S-n-propyl-O-[4-nitro-2-(methoxycarbonylhydrazonomethyl)phenyl]thio phosphate
O-ethyl-S-n-propyl-O-[4-chloro-2-(methoxycarbonylhydrazonomethyl)phenyl]thi ophosphate
O-ethyl-S-n-propyl-O-[4-nitro-2-(methoxyminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-chloro-2-(methoxyminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-nitro-2-(acetylhydrazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-chloro-2-(acetylhydrazonomethyl)phenyl]thiophosphat e
O-ethyl-S-n-propyl-O-[4-(oxamoylhydrazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphat e
O-ethyl-S-n-propyl-O-(1-methoxyiminomethyl-2-naphthyl)thiophosphate
O-ethyl-S-n-propyl-O-[4-methoxy-2-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-methoxy-2-(acethylhydrazonomethyl)phenyl]thiophosph ate
O-ethyl-S-n-propyl-O-[4-methoxy-2-(methoxycarbonylhydrazonomethyl)phenyl]th iophosphate
O-ethyl-S-n-propyl-O-[4-methoxy-2-(methoxyiminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(oxamoylhydrazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(methoxyiminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(ethoxyiminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-chloro-4-(methoxyiminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-(methoxyiminomethyl)phenyl]dithiophosphate
O-ethyl-S-n-butyl-O-[4-(methoxyiminomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[3-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-butyl-O-[2-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[4-(thiosemicarbazonomethyl)phenyl]dithiophosphate
O-ethyl-S-n-propyl-O-[2,6-dichloro-3-(semicarbazonomethyl)-phenyl]thiophosp hate
O-ethyl-S-n-propyl-O-[2-chloro-3-(semicarbazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(acetylhydrazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(cyanoacetylhydrazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(2-furoylhydrazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-propyl-O-[2-(ethoxycarbonylhydrazonomethyl)phenyl]thiophosphate
O-ethyl-S-n-butyl-O-[2,6-dichloro-4-(semicarbazonomethyl)phenyl]thiophospha te
O-ethyl-S-n-butyl-O-[4-(methoxycarbonylhydrazonomethyl)phenyl]thiophosphate
Selected species of the new compounds were evaluated to determine their pesticidal activity against mites, mite eggs, an aphid, a caterpillar, a beetle, and a fly.
Suspensions of the test compounds were prepared by dissolving one gram of compound in 50 ml of acetone in which had been dissolved 0.1 g (10 percent of the weight of the compound) of an alkylphenoxy polyethoxyethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into 150 ml of water to give roughly 200 ml of a suspension containing the compound in finely divided form. The thus-prepared stock suspension contained 0.5 percent by weight of compound. The concentrations in parts per million by weight employed in the tests described hereinbelow were obtained by appropriate dilutions of the stock suspension with water. The test procedures were as follows:
Adults and nymphal stages of the bean aphid (Aphis fabae Scop.) reared on potted dwarf nasturtrium plants at 68°-70° F. and 50±5 percent relative humidity, constituted the test insects. For testing purposes, the number of aphids per pot was standardized to 100-150 by trimming plants containing excess aphids.
The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation.
The potted plants (one pot per compound tested) infested with 100-150 aphids were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet the plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. After spraying, the pots were placed on their sides on a sheet of white standard mimeograph paper which had been previously ruled to facilitate counting. Temperature and humidity in the test room during the 24 hour holding period were 68°-70° F. and 50±5 percent, respectively. Aphids which fell onto the paper and were unable to remain standing after being uprighted were considered dead. Aphids remaining on the plant were observed closely for movement and those which were unable to move the length of the body upon stimulation by prodding were considered dead. Percent mortality was recorded for various concentration levels.
Larvae of the southern armyworm (Spodoptera eridania, (Cram.)), reared on Tendergreen bean plants at a temperature of 80+5° F. and a relative humidity of 50±5 percent, constituted the test insects.
The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Potted Tendergreen bean plants of standard height and age were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulations by use of a DeVilbiss spray gun set at 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. When dry, the paired leaves were separated and each one was placed in a 9 centimeter Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes were closed. The closed dishes were labeled and held at 80°-85° F. for three days. Although the larvae could easily consume the whole leaf within twenty-four hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation by prodding, were considered dead. Percent mortality was recorded for various concentration levels.
Fourth instar larvae of the Mexican bean beetle (Epilachna varivestis, Muls.), reared on Tendergreen bean plants at a temperature of 80±5 F. and 50±5 percent relative humidity, were the test insects.
The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. Tendergreen bean plants of standard height and age were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig air pressure. This application, which lasted 25 seconds, was sufficient to wet plants to run-off. As a control, 100-110 milliliters of a water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. When dry, the paired leaves were separated and each was placed in a 9 centimeter Petri dish lined with moistener filter paper. Five randomly selected larvae were introduced into each dish, and the dishes were closed. The closed dishes were labeled and held at a temperature of 80+5 F., for three days. Although the larvae could easily consume the leaf within 24 to 48 hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation, were considered dead.
The test organism was the egg of the Southern armyworm (Spodoptera eridania (Cram.)) as obtained from adults reared on Tendergreen bean plants at a temperature of 80°±5° F. and a relative humidity of 50±5 percent. The eggs were laid on freezer paper (Marlon 717, Copco paper). The paper was then cut into small sections containing one or two egg masses.
The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. The egg masses were dipped until they were thoroughly wet (5-10 seconds). They were then placed on a paper towel face up and were allowed to dry for 15-30 minutes. The dry eggs were placed in a 15×60 mm petri dish containing a cotton dental wick saturated with a 5 percent sodium chloride solution to maintain a high level of humidity. The closed dishes were labeled and held at a temperature of 80°±5° F. for four days. Larvae that emerged from the eggs, even if dead at the time of observation, were recorded as hatched.
Adults and nymphal stage of the two-spotted mite (Tetranychus urticae Koch), reared on Tendergreen bean plants at 80±5 percent relative humidity, were the test organisms. Infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-a-half inch clay pot. 150-200 mites, a sufficient number for testing, were transferred from the excised leaves to the fresh plants in a period of twenty-four hours. Following the twenty-four hour transfer period, the excised leaves were removed from the infested plants. The test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation. The potted plants (one pot per compound) were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 psig. air pressure. This application, which last 25 seconds, was sufficient to wet the plants to run-off. As a control, 100-110 milliliters of a water solution containing acetone and emulsifier in the same concentrations as the test compound formulations, but containing no test compound, were also sprayed on infested plants. The sprayed plants were held at 80±5 percent relative humidity for six days, after which a mortality count of motile forms was made. Microscopic examination for motile forms was made on the leaves of the test plants. Any individual which was capable of locomotion upon prodding was considered living.
Four to six day old adult house flies (Musca domestica, L.), reared according to the specifications of the Chemical Specialties Manufacturing Association (Blue Book, McNair-Dorland Co., N.Y. 1954; pages 243-244, 261) under controlled conditions of 80°±5° F. and 50±5 percent relative humidity, were the test insects. The flies were immobilized by anesthetizing with carbon dioxide and twenty-five immobilized individuals, males and females, were transferred to a cage consisting of a standard food strainer about five inches in diameter which was inverted over a wrapping-paper-covered surface. The test compounds were formulated by diluting the stock suspension with a 10 percent (by weight) sugar solution to give a suspension containing 500 parts of test compound per million parts of final formulation, by weight. Ten milliliters of the test formulation were added to a souffle cup containing a one-inch square of an absorbent cotton pad. This bait cup was introduced and centered on the blotting paper under the good strainer prior to admitting the anesthetized flies. The caged flies were allowed to feed on the bait for twenty-four hours, at a temperature of 80±5° F. and a relative humidity of 50±5 percent. Flies which showed no sign of movement on prodding were considered dead.
The results of these tests together with physical properties of the tested compounds are set forth in Table I below. In these tests the pesticidal activity of the compounds at the indicated dosage rate against aphid, mite, Southern Armyworm, Bean Beetle, and housefly was rated as follows:
A=excellent control
B=partial control
C=no control at 500 ppm.
The compounds contemplated in this invention may be applied as insecticides and miticides according to methods known to those skilled in the art. Pesticidal compositions containing the compounds as the active toxicant will usually comprise a carrier and/or diluent, either liquid or solid.
Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents. Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the acid of suitable surface active emulsifying and dispersing agents.
The choice of dispersing and emulsifying agents and the amount employed is dictated by the nature of the composition and ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not re-emulsify the toxicant after it is applied to the plant and wash it off the plant. Non-ionic, anionic, amphoteric, or cationic dispersing and emulsifying agents may be employed, for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary ammonium compounds, and the like.
In the preparation of wettable powder, dust or granulated compositions, the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like. In the formulation of the wettable powders the aforementioned dispersing agents as well as lignosulfonates can be included.
The required amount of the toxicants contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent. The concentration in the liquid concentrate will usually vary from about 10 to 95 percent by weight and in the solid formulations from about 0.5 to about 90 percent by weight. Satisfactory sprays, dusts, or granules for general use contain from about 1/4 to 15 pounds of active toxicant per acre.
The pesticides contemplated herein control the population of insects, mites and of ova mites and insects upon plants or other material to which the pesticides are applied. Generally, when used in sufficient amount to kill or repel the insects, they do not burn or injure the plant. The toxicants are compatible with substantially any other constituents of the spray schedule, and they may be used in the soil, upon the seeds, or the roots of plants without injuring either the seeds or roots of plants. They may also be used in combination with other pesticidally active compounds.
| TABLE I |
| Biological and Analytical Properties of the Compounds of this Invention S |
| TRUCTURE |
| ##STR7## |
| BIOLOGICAL ACTIVITYSOUTHERNMEXICAN R1 R2 R3 ANALYTICAL |
| BEAN APHID MITE ADULT ARMY WORM BEAN BEETLE HOUSEFLY |
| 4-CHNNHCONH2 H H C13 H20 N3 O4 PS B A A A A |
| Calc: C, 45.21; H, 5.85 Found: C, 45.39; H, 5.77 mp (°C.): |
| 118.5-122 2-CHNNHCOCONH2 H H C14 H20 N3 O5 PS C |
| A A A A Calc: C, 45.04; H, 5.41 Found: C, 45.33; H, 5.44 mp |
| (°C.): 148-150.5 2-CHNOCH3 H H C13 H20 NO4 PS |
| A A A A A Calc: C, 49.20; H, 6.36 Found: C, 49.63; H, 6.52 OIL |
| 3-CHNNHCONH2 H H C13 H20 N3 O4 PS C A A A A |
| Calc: C, 45.21; H, 5.85 Found: C, 47.13; H, 6.55 OIL 2-CHNNHCOCH.su |
| b.3 H H C14 H21 N2 O4 PS C A A A A Calc: C, |
| 48.83; H, 6.16 Found: C, 48.80; H, 6.17 OIL 2-CHNNHCOCH2 CN H |
| H C15 H20 N3 O4 PS C A A A A Calc: C, 48.80; H, |
| 5.47 Found: C, 48.05; H, 5.58 mp (°C.): 103-110 |
| ##STR8## |
| H H C17 H21 N2 O5 PSCalc: C, 51.51; H, 5.35Found: |
| C, 50.59; H, 4.52Oil C A A A A 2-CH NNHCO2 CH2 CH3 H H |
| C15 H23 N2 O4 PS A A A A A Calc: C, 48.12; H, |
| 6.20 Found: C, 44.92; H, 6.44 Oil 2-CHNNHCONH2 4-Cl H |
| C13 H19 ClN3 O4 PS B A A A A Calc: C, 41.11; H, |
| 5.05 Found: C, 41.67; H, 4.94 mp (°C.): 112-116 2-CHNNHCONH. |
| sub.2 4-NO2 H C13 H14 N4 O6 PS B A A A A |
| Calc: C, 40.00; H, 4.92 Found: C, 38.24; H, 4.78 mp (°C.): |
| 105-109.5 4-CHNNHCONH2 2-OCH3 H C14 H22 N3 |
| O3 PS C C A A A Calc: C, 44.79; H, 5.91 Found: C, 44.99; H, |
| 5.87 mp (°C.): 133-138 4-CHNOCH3 H H C13 H20 |
| NO4 PS A A A A A Calc: C, 49.20; H, 6.35 Found: C, 49.35; H, |
| 6.42 Oil 3-CHNNHCONH2 4-NO2 H C13 H19 N4 |
| O6 PS C A A A A Calc: C, 40.00; H, 4.91 Found: C, 38.5; H, |
| 4.67 mp (°C.): 128-131 4-CHNNHCONH2 2-NO2 6-OCH3 |
| C14 H21 N4 O7 PS A A A A A Calc: C, 40.00; H, |
| 5.04 Found: C, 39.30; H, 5.26 mp (°C.): 149-154 2-CHNNHCO.su |
| b.2 CH3 H H C14 H21 N2 O5 PS A A A A A Calc: |
| C, 46.66; H, 5.88 Found: C, 46.72; H, 6.38 OIL 2-CHNNHCO2 |
| C(CH3)3 H H C17 H27 N2 O5 PS A C A A A |
| Calc: C, 50.73; H, 6.76 Found: C, 49.49; H, 7.20 OIL 2-CHO |
| 4-NO2 H C12 H16 NO6 PS A A A A A Calc: C, 43.24; |
| H, 4.85 Found: C, 42.53; H, 5.23 OIL 3-CHO 4-NO2 H C12 |
| H16 NO6 PS A A A A A Calc: C, 43.25; H, 4.84 Found: C, |
| 40.98; H, 4.95 OIL 4-CHO 2-NO2 6-OCH3 C13 H18 |
| NO7 |
| PS A A A A A Calc: C, 42.98; H, 5.00 OIL 4-CHO 2-OCH3 H |
| C13 H19 O5 PS A A A B A Calc: C, 49.05; H, 6.03 |
| Found: C, 47.23; H, 6.17 OIL 2-CHO 4-OCH3 H C13 H19 |
| O5 PS A A A A A Calc: C, 49.05; H, 6.03 Found: C, 48.49; H, |
| 6.10 OIL |
| 2-CHO |
| ##STR9## |
| C16 H19 O4 PSCalc: C, 56.80; H, 5.67Found: C, 56.41; H, |
| 5.95OIL A A A A A |
| 2-CHNNHCONH2 |
| ##STR10## |
| C17 H22 N3 O4 PSCalc: C, 51.65; H, 5.57Found: C, |
| 52.33; H, 5.54OIL C A A A A 2-CHNNHCONH2 H H C13 H20 |
| N2 OPS C A A A A Calc: C, 45.22; H, 5.80 Found: C, 45.36; H, |
| 5.72 mp (°C.): 127-129 |
| 2-CHO |
| ##STR11## |
| C17 H21 O4 PS (Sn-butyl)Calc: C, 57.94; H, 4.86Found: |
| C, 57.04; H, 6.18OIL A A A A A 2-CHNNHCSNH2 H H C13 H20 |
| N3 O3 PS2 C A A B A Calc: C, 43.70; H, 5.58 Found: |
| C, 44.64; H, 5.51 OIL |
| ##STR12## |
| H H C17 H29 ClN3 O4 PS Calc: C, 46.63; H, 6.63OIL C |
| A A C A 4-CHNOCH3 2-Cl 6-Cl C13 H18 Cl2 NO4 PS |
| A A A A A Calc: C, 40.43; H, 4.71 Found: C, 40.72; H, 4.69 OIL |
| 4-CHNNHCONH2 2-Cl 6-Cl C13 H17 Cl2 N3 O4 |
| PS A A A A A Calc: C, 37.78; H, 4.16 Found: C, 37.72; H, 4.15 |
| mp (°C.): 130-133 4-CHNNHCO2 CH3 2-Cl 6-Cl C14 |
| H19 Cl2 N2 O5 PS B A A A A Calc: C, 39.17; H, |
| 4.47 Found: C, 37.76; H, 4.50 mp (°C.): 83-85 2-CHNNHCO |
| 2 CH3 4-NO2 H C14 H19 N3 O7 PS C A A A A |
| Calc: C, 41.48; H, 4.73 Found: C, 41.21; H, 4.99 mp (°C.): |
| 92-95 2-CHNNHCO2 CH3 4-Cl H C14 H 20 ClN2 |
| O5 PS B A A A A Calc: C, 42.59; H, 5.11 Found: C, 42.48; H, |
| 5.03 mp (°C.): 98-103 2-CHNOCH3 4-NO2 H C13 |
| H19 N2 O6 PS A A A A A Calc: C, 43.09; H, 5.30 |
| Found: C, 43.89; H, 5.40 OIL 4-CHNNHCSNHCH2 CHCH2 H H |
| C16 H24 N3 O3 PS2 C A A A A Calc: C, 47.86; |
| H, 6.03 Found: C, 48.12; H, 6.12 OIL 2-CHNNHCO2 CH3 |
| 4-OCH3 H C15 H23 N2 O6 PS C A A A A Calc: C, |
| 46.14; H, 5.95 Found: C, 45.00; H, 6.51 OIL 2-CHNNHCOCH3 |
| 4-OCH3 C15 H23 N2 O5 PS A A A A A Calc: C, |
| 48.11; H, 6.20 Found: C, 47.37; H, 6.27 mp (°C.): 75-78 N |
| 2-CHNHCONH2 4-OCH3 H C14 H22 N3 O5 PS C A |
| A A A Calc: C, 44.79; H, 5.91 Found: C, 45.52; H, 5.93 mp |
| (°C.): 113-117 4-CHNOCH2 C6 H5 H H C19 |
| H24 NO4 PS A A A A A Calc: C, 58.00; H, 6.16 Found: C, |
| 57.60; H, 5.82 OIL 2-CHNOCH3 4-OCH3 H C14 H22 |
| NO5 PS A A A A A Calc: C, 48.41; H, 6.39 Found: C, 51.39; H, |
| 6.98 OIL 4-CHNNHCONH2 2-Br 6-Br C13 H18 Br2 |
| N3 O4 PS A A A A A Calc: C, 31.03; H, 3.61 Found: C, |
| 31.06; H, 3.55 mp (°C.): 155-156 4-CHNNHCO2 CH3 2-Br |
| 6-Br C14 H19 Br2 N2 O5 PS C A A A A Calc: C, |
| 32.45; H, 3.70 Found: C, 33.63; H, 3.80 OIL 4-CHNOCH3 2-Br |
| 6-Br C13 H18 Br2 NO4 PS A A A A A Calc: C, 32.86; |
| H, 3.83 Found: C, 33.13; H, 3.88 OIL |
| ##STR13## |
| H H C19 H22 Cl2 NO4 PSCalc: C, 49.35; H, 4.81Found: |
| C, 49.38; H, 4.88OIL A A A A A |
| ##STR14## |
| H H C19 H22 Cl2 NO4 PSCalc: C, 49.35; H, 4.81Found: |
| C, 49.42; H, 4.91OIL A A A A A |
| ##STR15## |
| 2-Cl 6-Cl C19 H20 Cl4 NO4 PSCalc: C, 42.96; H, |
| 3.80Found: C, 42.89; H, 3.91 OIL A A A A A 4-CHC(CN)2 H H C15 |
| H17 N2 O3 PS C A A A A Calc: C, 53.56; H, 5.10 |
| Found: C, 51.02; H, 5.11 mp (°C.): 60-70 2-CHNOCH3 4-Cl H |
| C13 H19 ClNO4 PS A A A A A Calc: C, 44.38; H, 5.45 |
| Found: C, 44.60; H, 5.90 OIL 2-CHNNHCOCH3 4-NO2 H C14 |
| H20 N3 O6 PS A A A A A Calc: C, 43.19; H, 5.19 |
| Found: C, 43.39; H, 5.40 mp (°C.): 157-160 2-CHNNHCOCH3 |
| 4-Cl H C14 H20 ClN2 O4 PS A A A A A Calc: C, |
| 44.43; H, 5.34 Found: C, 44.68; H, 5.25 mp (°C.): 105-108 |
| 4-CHNNHCOCONH2 H H C14 H20 N3 O5 PS C A A A A |
| Calc: C, 45.03; H, 5.41 Found: C, 44.28; H, 5.33 mp (°C.): |
| 218-220 4-CHNNHCO2 CH3 H H C14 H21 N2 O5 |
| PS B A A A A Calc: C, 46.66; H, 5.88 Found: C, 46.91; H, 6.03 |
| OIL |
| 2-CHNOCH3 |
| ##STR16## |
| C17 H22 NO4 PSCalc: C, 55.57; H, 6.04Found: C, 56.66; |
| H, 6.02OIL A A A A A |
In Table II, Examples A through C are compounds found in the prior art. Examples D through F, are compounds of this invention. Comparisons of the pesticidal properties of each are illustrative of the surprisingly and significantly enhanced effectiveness achieved with the utilization of the compounds of this invention.
Similarly, comparisons of the prior art compound of Example G of Table II to Examples H and I--compounds of this invention--illustratively show the increased pesticidal effectiveness realized with the compounds of this invention.
| TABLE II |
| __________________________________________________________________________ |
| BIOLOGICAL ACTIVITY LD50 (ppm) |
| SOUTHERN |
| MEXICAN |
| BEAN MITE ARMY BEAN |
| EX. |
| STRUCTURE APHID |
| ADULT |
| WORM BEETLE HOUSEFLY |
| __________________________________________________________________________ |
| ##STR17## 70 25 80 500 130 |
| B |
| ##STR18## 15 i 108 i 58 |
| C |
| ##STR19## 200 32 300 500 450 |
| D |
| ##STR20## i 4 7 46 9 |
| E |
| ##STR21## i 3 9 15 9 |
| F |
| ##STR22## 180 1 16 20 16 |
| G |
| ##STR23## 25 12 105 150 30 |
| H |
| ##STR24## 20 20 20 12 13 |
| I |
| ##STR25## 500 3 12 15 7 |
| __________________________________________________________________________ |
Hodakowski, Leonard E., Wilson, II, Charles A.
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